Emulsifying agents and process of making same



Patented Apr. 18, 1939 UNITED STATES PATENT OFFICE EMULSIFYING AGENTSAND PROCESS OF MAKING SAME No Drawing.

Application May 4, 1936,

Serial No. 77,829

Claims.

This invention relates to improvements in emulsifying agents, and moreparticularly to emulsifying agents adapted for use in the preparation ofstable bitumen emulsions, e. g. asphalt emulsions.

Heretofore, bitumen emulsions have been prepared by the use of aqueousrosin soap solutions, but such bitumen emulsions have been characterizedby having little stability, and tendency to break down into theircomponents in a comparatively short time or by the addition ofelectrolytes. Bitumen emulsions have also been prepared heretofore bythe use of aqueous solutions of saponified oxidized resins and oxidizedrosin obtained from the furfural refining of gasoline solutions ofrosin, obtained by the gasoline extraction of resinous wood, without,however, a'c-- complishing the desired result of rendering the bitumenemulsions made therewith stable over long periods of time and stableagainst the addition of electrolytes.

In accordance with our invention, a product having superior emulsifyingproperties is prepared by the treatment with an excess of caustic alkalisolution, e. g. sodium or potassium hydroxide of a product of therefining of wood rosin. This product of the refining of wood rosin hasnot yet been analyzed completely to with or without preliminary steamingto remove therefrom turpentine and pine oil, is extracted with a solventwhich is a solvent for the wood rosin, turpentine, and pine oilcontained in the pine wood chips, and which is also a solvent'for othercomplex substances contained in the pine wood chips. Such a solvent maybe, for example, a coal tar hydrocarbon, such as benzene, toluene,xylene, etc. chips may be accomplished by flooding the chips with thesolvent, with or without the use of heat.

When the extraction of the wood chips has been sufficient, the coal tarhydrocarbon solution of matter extracted from the chips is drawn off thechips and the solvent evaporated and reused in the process, if desired.Evaporation of the solvent leaves turpentine, pine oil, rosin, and theresin the object of this invention. The tur- The extraction of the woodpentine and pine oil are then removed by distillation, leaving a darkcolored resin comprising a mixture of FF Wood rosin and the resin whichis the object of this invention. This resinous mixture is then extractedwith a substance which is a solvent for the FF rosin but not a solventfor the other resin present in the mixture. As such solvent we may use,for example, and preferably at an elevated temperature, petroleumhydrocarbons such as petroleum ether, gasoline, heptane, hexane, etc.,or an operaole equivalent therefor.

When the mixture of resinous materials has been sufficiently extractedby the petroleum hydrocarbon, a dark colored, resinous substanceremains, which, when freed from occluded gasoline or other petroleumhydrocarbon, is the resin we use in the preparation of our improvedemulsifying agent. Such a resin is characterized by a methoxy content ofabout 3 to 6%, naphtha-insoluble matter about 98%, melting, point about115 0., by the drop method, and acid number 100.

We then sapohify, preferably with the use of heat, the resin, prepared,for example, as.above, by the use of aqueous potassium hydroxidecontaining, for example, 8 to 18% potassium hydroxide, based on theresin used. Such saponifled resin solutions will contain, for example,

45 to 55% water and from 0 to 5% free caustic potash. These improvedemulsifying agents may be used to advantage in the preparation ofbitumen emulsions which are not subject to precipitation on addition ofwater-containing electrolytes. As an example of such.improved bitumenemulsions, asphalt emulsions containing rosin soap, and asphaltemulsions containing our improved emulsifying agent, designated in thefollowing table as resin soap, were prepared At time of making theemulsion.

The demulsibility tests were made as follows:

(a) To 100 g. of asphalt emulsion add 35 cc. of 0.02 normal calciumchloride solution, with stirring, during 2 minutes, wash the residuethrough a 20 mesh sieve, and weigh the residue. The ratio of residueremaining, to the asphalt content of the emulsion, is the per cent.demulsibility.

' (b) To 100 g.'of asphalt emulsion add 50 cc. of 0.1 normal calciumchloride solution, with stirring, during 2 minutes, wash the residuethrough a 20 mesh sieve, and weigh the residue.

We do not limit our new emulsifying agent to use with bitumens, toproduce bitumen or asphalt emulsions, but may use the same. in any Forexample, we may use our improved emulsifying agent in the preparation ofstable emulsions of petroieum ils', vegetable oils, waxes,nitrocellulose solutions, etc. What we desire to claim ters Patent is: I

1. Process of manufacture of an emulsifying agent comprising saponifyingwith an aqueous alkali metal hydroxide the resin obtained by extractingfpine wood with a coal tar hydrocarbon, removing'volatile substances fromsaid extract, and removing wood rosin from the remaining solid resinousmixtures by extraction with a petroleum hydrocarbon said resin beingalso characterized by having a methoxy content of about 3% to about 6%,naphtha-insoluble matter about 98%, melting point about C. and acidnumber about 100. 2. ,P rocess or manufacture of an emulsifyingagentecomprising saponifying with an excess of an aqueous alkali metalhydroxide the resin obtained by extracting pine wood chips with "a coaltar-hydrocarbon, removing volatile substances and protect by Let-.Patent no. 2,155,1t1.

' CORNELIS The ratio of residue remaining, to the asphalt connectionwhere a stable emulsion is desired.

CERTIFICATE OF CORRECTION from said extract, and removing wood rosinfrom the remaining solid resinous mixture by extraction with a petroleumhydrocarbon saidresin being also characterized by having a methoxycontent of about 3% to about 6%, naphthainsoluble matter about 98%,melting point about 115 C. and acid number about 100. 3. An emulsifyingagent comprising the re action product of an aqueous alkali metalhydroxide and a resin obtained by extracting pine wood by a coal tarhydrocarbon, removing volatile substances from the extract andextracting the non-volatile residue with a petroleum hydrocarbon saidresin being also characterized by having a methoxy content of about 3%to about 6%, naphtha-insoluble matter about 98%, melting point about 115C. and acid number about 4. An emulsifying agent comprising the reactionproduct of an aqueous alkali metal hydroxide and a resin obtained byextracting pine wood by a coal tar hydrocarbon, removing volatilesubstances from the extract and removing wood rosin from thenon-volatile residue by extraction with petroleum hydrocarbon said resinbeing also characterizedby having .a methoxy content of about 3% toabout 6%, naphtha-l insoluble matter about 98%, melting point abou 115C. and acid number about 100.

5. As an emulsifying agent the reaction product of an aqueous alkalimetal hydroxide and a resin characterized by a methoxy content of about3-6% and naphtha-insoluble. matter about 98% melting point about 115 C.and acid number about 100.

CORNELIS MATERS. MAR'I'INUS JOHANNES RIEMERSMA.

April 1 19 9.- MATERS, ET AL.

It is hereby certified that errorappears in the printed specification ofthe above numbered patent requiring correction as follows: Page -l, sec-0nd column, line 11, for "operaole" read operable; lines 1 1 to' 51, inthe table, left hand column thereof,

"Resin soap. Do.... Don't-H for SOB-p. me e e e a DOOIIOIOOIOI.

read Do..

Rosin soap. Resin soap.

and that the said etter-s Patent should be read with this correctiontherein that thesame may conform to-the record ofthe case in the PatentOffice. .signed-andsealed this 8th day of August, A. D'. 1959. 1

(Seal) Leslie Frazer, Acting Commissioner of Patents.

